CN113072062B - Graphene quantum dot/ZnO/chlorella composite film and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a graphene quantum dot/ZnO/chlorella composite film and a preparation method and application thereof, wherein the film comprises 15-21% zinc oxide nano crystal grains, 60-69% carbonized chlorella, 4-10% graphene quantum dots and 2-10% platinum nano particles; the preparation method of the film comprises the following steps: (1) preparing carbonized chlorella; (2) preparing a platinum nanoparticle low-carbon alcohol solution; (3) Adding a zinc precursor and graphene quantum dots into low-carbon alcohol, uniformly stirring, performing ultrasonic dispersion, adding platinum nano particles, and performing ultrasonic dispersion uniformly to obtain a mixed solution; (4) Adding carbonized chlorella, and uniformly stirring to obtain a mixed solution; (5) Spin-coating the mixed solution on a device substrate with interdigital electrodes, and sequentially performing post heat treatment and oxygen plasma treatment; and (6) heat treatment to obtain the composite film. The film has high sensitivity, low detection limit, 3.3 sensitivity to 50ppb concentration of methanol and excellent selectivity to methanol.
Description
Technical Field
The invention relates to a composite film and a preparation method and application thereof, in particular to a graphene quantum dot/ZnO/chlorella composite film and a preparation method and application thereof.
Background
Air pollution, water pollution and soil pollution are three pollution which threaten normal life of human beings, and in recent years, along with development of industry and population increase, the air pollution becomes more and more serious, especially, the indoor volatile organic compounds VOCs pollute, and moreover, people are in the room for most of time, and the exceeding of the standard of the VOCs seriously threatens the healthy life of common people. In addition, certain endogenous VOCs in trace amounts of volatile organic compounds in exhaled breath of humans can serve as clinical biomarkers. In current complex air contaminated environments, accurate calibration of endogenous VOCs in exhaled breath is important, both for analysis of exhaled breath and for environmental exposure assessment. Wherein methanol in the exhaled breath has been identified as a biomarker for neurological disease. The semiconductor gas sensor is a common gas sensor, and is widely applied to places needing to monitor gas in real time because of the advantages of microminiaturization, real-time monitoring, simple use, low price, higher precision and the like; however, gas sensors based on metal oxide semiconductors often require higher operating temperatures (200-400 ℃) to obtain better sensing performance of the devices, and gas sensitive materials of the gas sensors often have poor gas sensitive performance, unstable and reliable response, low corresponding speed, low sensitivity and poor selectivity.
Disclosure of Invention
The invention aims to: the invention aims to provide a graphene quantum dot/ZnO/chlorella composite film with high sensitivity, high specificity and low interference performance, and another aim of the invention is to provide a preparation method of the composite film and to provide application of the composite film.
The technical scheme is as follows: the graphene quantum dot/ZnO/chlorella composite film comprises 15-21% of zinc oxide nano crystal grains, 60-69% of carbonized chlorella, 4-10% of graphene quantum dots and 2-10% of platinum nano particles.
The graphene quantum dots are nitrogen doped graphene quantum dots, chlorinated graphene quantum dots or sulfur doped graphene quantum dots, the particle size of the carbonized chlorella is 200-1 um, the size of the zinc oxide nano crystal particle is 3-4 nm, the particle size of the functionalized graphene quantum dots is 4-6 nm, and the particle size of the platinum nano particles is 4-8 nm.
The preparation method of the graphene quantum dot/ZnO/chlorella composite film comprises the following steps:
(1) Preparing carbonized chlorella; (2) Preparing platinum nano particles by using chloroplatinic acid, and preparing a platinum nano particle low-carbon alcohol solution;
(3) Adding a zinc precursor and graphene quantum dots into low-carbon alcohol, uniformly stirring, performing ultrasonic dispersion, adding platinum nano particles, and performing ultrasonic dispersion uniformly to obtain a mixed solution;
(4) Rotary evaporating the mixed solution, concentrating to 1/4-1/2, adding carbonized chlorella, and stirring uniformly to obtain a mixed solution;
(5) Spin-coating the mixed solution on a device substrate with interdigital electrodes, heating and drying, and then sequentially carrying out post heat treatment and oxygen plasma treatment to obtain a dried sample;
(6) And (3) placing the dried sample under inert gas for heat treatment to obtain the graphene quantum dot/ZnO/chlorella composite film.
Wherein, step 2 comprises the following steps:
(21) Adding the materials with the volume ratio of 1:1.2 to 2.4:5, a chloroplatinic acid solution, a PVP solution and dimethylsulfoxide DMSO are uniformly mixed, wherein the concentrations of the chloroplatinic acid solution and the PVP solution are respectively 5 multiplied by 10 -3 ～5×10 -2 mol/L、1×10 -4 ～1×10 -3 mol/L；
(22) Adding 6×10 concentration to the mixed solution -3 ～6×10 -2 Heating and stirring a sodium ascorbate solution with mol/L, wherein the volume ratio of the sodium ascorbate solution to the chloroplatinic acid solution is 1.5-2: 1, a step of;
(23) Carrying out centrifugal separation, acetone cleaning and ethanol cleaning on a sample to obtain platinum nano particles;
(24) Dispersing the platinum nano particles into low-carbon alcohol under the action of ultrasound to obtain a platinum nano particle low-carbon alcohol solution.
Wherein the zinc precursor in the step 3 is zinc acetate, zinc acrylate or zinc methacrylate, the graphene quantum dots are nitrogen-doped graphene quantum dots, chlorinated graphene quantum dots or sulfur-doped graphene quantum dots, and the low-carbon alcohol is at least one of ethylene glycol, propanol and isopropanol.
Wherein, in the step 3, the mass ratio of the zinc precursor to the graphene quantum dots is 25-130: 1-5, the mass ratio of the graphene quantum dots to the platinum nano particles is 12-18: 3 to 5.
Wherein, the mass ratio of the carbonized chlorella to the platinum nano particles in the step 4 is 6-12: 1.
the graphene quantum dot/ZnO/chlorella composite film can be used as a sensitive layer to be applied to a gas sensor, wherein the gas sensor is a methanol gas sensor.
Working principle: the method is characterized in that a post-heat steaming method is used in the process of forming the composite film, so that the chlorella, the zinc oxide quantum dots and the graphene quantum dots form heterojunctions stably, the relative positions of the chlorella, the zinc oxide quantum dots and the graphene quantum dots are fixed in the preparation process, therefore, the chlorella, the graphene quantum dots and the zinc oxide nano-crystalline grains can be uniformly distributed in the composite film to form a plurality of heterojunctions, the composite film has a larger specific surface area, meanwhile, the chlorella and the zinc oxide form a plurality of protrusions on the surface of the composite film, the contact of the film and gas is enhanced, the chlorella has a multi-stage structure, the diffusion of methanol is facilitated, the sensing response occurs at the heterojunctions interface, in addition, the nano-pores formed by stacking the zinc oxide nano-crystalline grains form a multi-stage structure formed by the composite sensing material, the interfaces exist between the quantum crystalline grains and the chlorella, the interface energy is larger, the resistance is also larger, and the resistance change of the chlorella when the chlorella responds to VOCs gas is larger, and the chlorella has higher sensitivity than other nano-materials.
The beneficial effects are that: compared with the prior art, the invention has the remarkable advantages that: 1. high sensitivity, low detection limit, and 3.3 sensitivity to 50ppb methanol; 2. can detect a plurality of VOCs gas types, and has good repeatability; 3. the methanol has excellent selectivity, and the response and recovery speed are high, wherein the response and recovery time are both within 10 seconds; 4. the device has small volume, can realize miniaturization and integration of the device, and has low manufacturing cost.
Drawings
FIG. 1 is an SEM image of example 1;
fig. 2 is a scanning electron microscope image of example 1: (a) a TEM image; (b) HRTEM images;
FIG. 3 is an X-ray diffraction pattern of example 1;
FIG. 4 is a Raman diagram of example 1;
fig. 5 is a performance test chart of example 1: (a) a plot of n-butanol response to different concentrations; (b) fitting the map;
FIG. 6 is a chart of the sensor selectivity test of example 1;
FIG. 7 is a graph of a sensing performance fit for example 2;
FIG. 8 is a chart of the sensor selectivity test of example 2;
FIG. 9 is a graph of a sensing performance fit for example 3;
fig. 10 is a sensor selectivity test chart of example 3.
Detailed Description
Example 1
(1) Placing a ceramic boat containing chlorella into a tube furnace, vacuumizing, maintaining for 10 minutes, introducing nitrogen, maintaining the gas flow at 200SCCM, and roasting at 850 ℃ for 2 hours to obtain carbonized chlorella;
(2) 5mL of the mixture was added to a beaker at a concentration of 3.0X10 -2 Chloroplatinic acid solution with mol/L and 12mL concentration of 6×10 - 4 The mixture was stirred at 70℃for 10 minutes with 7.5mL of 3.0X10 s of DMSO and mol/L PVP solution - 2 Stirring a mol/L sodium ascorbate solution for 10 minutes at 70 ℃, cooling to room temperature, centrifugally separating a cooled sample, washing with acetone three times, and washing with ethanol once to obtain platinum nano particles; dispersing 15mg of platinum nano particles in 3mL of ethylene glycol by ultrasonic to obtain a platinum nano particle ethylene glycol solution with the concentration of 5 mg/mL;
(3) Adding 1g of zinc acetate and 70mg of nitrogen doped graphene quantum dots into 8mL of ethylene glycol, magnetically stirring for 30 hours at normal temperature, performing ultrasonic dispersion for 12 minutes, adding 1mL of platinum nanoparticle ethylene glycol solution with concentration of 5mg/mL, and performing ultrasonic dispersion for 12 minutes to obtain a mixed solution uniformly;
(4) Rotary evaporating the mixed solution, adding 40mg of carbonized chlorella when the solution is reduced to 3mL, adding carbonized chlorella, and stirring uniformly to obtain a mixed solution;
(5) Drying the substrate for 2 hours at about 70 ℃ after spin coating the coating, repeating the coating for 4 times and drying, putting the sample into a closed container, regulating the humidity in the container to 75% and the temperature to 120 ℃, taking out the device after 36 hours of treatment, and carrying out oxygen plasma treatment on the sensor device for 12 minutes at normal temperature, wherein the substrate is: a silicon substrate, silicon dioxide is deposited on the silicon substrate, a titanium layer and a platinum layer are deposited on the silicon substrate, and a Jin Cha finger electrode is etched on the surface;
(6) And (3) placing the sample in nitrogen and roasting for 2 hours at 400 ℃ to obtain the graphene quantum dot/ZnO/chlorella composite film.
As shown in FIG. 1, the chlorella carbide in the composite film is uniformly dispersed on the film material, the grain size is in the range of 200 nm-1 um, meanwhile, pt nano particles are uniformly dispersed in the film material, as shown in FIG. 2 (a), the chlorella carbide and zinc oxide film have good structures, the film itself has a mesoporous structure, the chlorella carbide itself has a porous structure, as shown in FIG. 2 (b), the zinc oxide nano particles are uniformly distributed, the grain size is 3-4 nm, as shown in FIG. 3, the zinc oxide crystal grain crystallinity is good, the grain size is 3.5nm, as shown in FIG. 4, the zinc oxide crystallinity in the composite film is good, the carbon material has a relatively large proportion in the composite material, the zinc oxide element is 15%, the Pt element is 5%, the chlorella carbide element is 70% and the graphene quantum dot element is 10% according to the analysis of surface elements.
And (3) testing the methanol response performance of the gas sensor of the graphene quantum dot/ZnO/chlorella composite film, operating the gas sensor under a certain current, after the initial baseline is stable, introducing methanol gas with corresponding concentration, after the resistance of the gas sensor is reduced and reaches balance, introducing air into the test cavity until the baseline is restored to be stable again, acquiring corresponding gas-sensitive test data by a computer, and completing the gas-sensitive test. The real-time response curves of the gas sensor of the graphene quantum dot/ZnO/chlorella composite film to methanol with the concentration of 50ppb-5ppm (50 ppb,100ppb,200ppb,300ppb,400ppb,500ppb,1ppm,2ppm, and 5 ppm) at 50 ℃ are shown in fig. 5 (a) and 5 (b), and it can be seen that the surface of the gas sensor of the graphene quantum dot/ZnO/chlorella composite film shows a rapid increasing trend along with the increase of the concentration of methanol gas, the sensitivity of the gas sensor of the graphene quantum dot/ZnO/chlorella composite film is increased from 3.3 to 26.2 when the concentration of methanol is increased from 50ppb to 5ppm, and the correlation characteristic of the gas sensor of the graphene quantum dot/ZnO/chlorella composite film to the output characteristic curve of methanol is good, and the response and recovery speed are high, wherein the response and recovery time are both within 10 seconds.
And (3) carrying out gas selectivity test on the gas sensor of the graphene quantum dot/ZnO/chlorella composite film, firstly, working the gas sensor of the graphene quantum dot/ZnO/chlorella composite film at 50 ℃, after the initial baseline is stable, then introducing 100ppb of methanol gas with the humidity of 90%, after the resistance of the gas sensor is reduced and reaches equilibrium, introducing air into a test cavity until the baseline is restored to be stable again, and completing the gas sensing test. Under the same test conditions, the ethanol, isopropanol, acetone, formaldehyde, benzene, toluene, diethyl ether and ammonia with the concentration of 100ppb are respectively introduced, and as can be seen from fig. 6, the sensitivity of the gas sensor to methanol is far higher than that of the gas sensor to ethanol, isopropanol, acetone, formaldehyde, benzene, toluene, diethyl ether and ammonia, and is more than 3 times that of other target gases, which indicates that the graphene quantum dot functionalized zinc oxide/chlorella composite gas sensor has excellent selectivity to methanol.
Example 2
(1) Placing a ceramic boat containing chlorella into a tube furnace, vacuumizing, maintaining for 10 minutes, introducing nitrogen, maintaining the gas flow at 200SCCM, and roasting at 800 ℃ for 2.5 hours to obtain carbonized chlorella;
(2) 5mL of the mixture was added to a beaker at a concentration of 3.0X10 -2 Chloroplatinic acid solution with mol/L and 6mL concentration of 6×10 - 4 The mixture was stirred at 70℃for 10 minutes with 7.5mL of 3.0X10 s of DMSO and mol/L PVP solution - 2 Stirring the sodium ascorbate solution with mol/L at 70 ℃ for 10 minutes, and coolingCooling to room temperature, performing centrifugal separation on the cooled sample, washing with acetone for three times, and washing with ethanol for one time to obtain platinum nano particles; dispersing 15mg of platinum nano particles in 3mL of ethylene glycol by ultrasonic to obtain a platinum nano particle ethylene glycol solution with the concentration of 5 mg/mL;
(3) Adding 1g of zinc acrylate and 70mg of sulfur-doped graphene quantum dots into 10mL of ethylene glycol, magnetically stirring for 36 hours at normal temperature, performing ultrasonic dispersion for 10 minutes, adding 1mL of platinum nanoparticle ethylene glycol solution with concentration of 5mg/mL, and performing ultrasonic dispersion for 15 minutes to obtain a mixed solution uniformly;
(4) Rotary evaporating the mixed solution, adding 30mg of carbonized chlorella when the solution is reduced to 5mL, adding carbonized chlorella, and stirring uniformly to obtain a mixed solution;
(5) Spin-coating a film on a substrate, drying at about 60 ℃ for 2 hours, repeating the film coating for 4 times, drying, placing a sample into a closed container, regulating the humidity inside the container to be 85% and the temperature to be 140 ℃, taking out the device after 32 hours of treatment, and carrying out oxygen plasma treatment on the sensing device for 10 minutes at normal temperature, wherein the substrate is: a silicon substrate, silicon dioxide is deposited on the silicon substrate, a titanium layer and a platinum layer are deposited on the silicon substrate, and a Jin Cha finger electrode is etched on the surface;
(6) And (3) placing the sample in nitrogen and roasting for 2.5 hours at the temperature of 350 ℃ to obtain the graphene quantum dot/ZnO/chlorella composite film.
The performance test diagrams are shown in fig. 7 and 8, and when the concentration of n-butyraldehyde gas is 20ppb-10ppm, the output characteristic curve of the graphene quantum dot functionalized zinc oxide/chlorella composite sensor on n-butyraldehyde also shows good correlation characteristics, and the sensitivity on n-butyraldehyde is far higher than that on ammonia, acetone, benzene, toluene, ethanol, diethyl ether and isopropanol, and is more than 4 times that of other target gases, so that the gas sensor has good selectivity on n-butyraldehyde gas.
Example 3
(1) Placing a ceramic boat containing chlorella into a tube furnace, vacuumizing, maintaining for 10 minutes, introducing nitrogen, maintaining the gas flow at 200SCCM, and roasting at 900 ℃ for 1.5 hours to obtain carbonized chlorella;
(2) 10mL of the mixture was added to a beaker at a concentration of 3.0X10 -2 Chloroplatinic acid solution with mol/L and 20mL concentration of 6×10 - 4 The mixture was stirred at 70℃for 8 minutes with 15mL of 3.0X10. DMSO and the PVP solution in mol/L - 2 Stirring a mol/L sodium ascorbate solution at 70 ℃ for 8 minutes, cooling to room temperature, centrifuging the cooled sample, washing with acetone three times, and washing with ethanol once to obtain platinum nano particles; dispersing 15mg of platinum nano particles in 3mL of ethylene glycol by ultrasonic to obtain a platinum nano particle ethylene glycol solution with the concentration of 5 mg/mL;
(3) Adding 1g of zinc methacrylate and 60mg of sulfur-doped graphene quantum dots into 6mL of ethylene glycol, magnetically stirring for 24 hours at normal temperature, performing ultrasonic dispersion for 15 minutes, adding 1mL of platinum nanoparticle ethylene glycol solution with concentration of 5mg/mL, and performing ultrasonic dispersion for 15 minutes uniformly to obtain a mixed solution;
(4) Rotary evaporating the mixed solution, adding 60mg of carbonized chlorella when the solution is reduced to 2mL, adding carbonized chlorella, and stirring uniformly to obtain a mixed solution;
(5) Spin-coating a film on a substrate, drying for 2 hours at about 80 ℃, repeating the film coating for 4 times, drying, placing a sample into a closed container, regulating the humidity in the container to be 95% and the temperature to be 160 ℃, taking out the device after 28 hours of treatment, and carrying out oxygen plasma treatment on the sensing device for 15 minutes at normal temperature, wherein the substrate is: a silicon substrate, silicon dioxide is deposited on the silicon substrate, a titanium layer and a platinum layer are deposited on the silicon substrate, and a Jin Cha finger electrode is etched on the surface;
(6) And (3) placing the sample in nitrogen and roasting for 1.5 hours at the temperature of 450 ℃ to obtain the graphene quantum dot/ZnO/chlorella composite film.
The performance test diagrams are shown in fig. 9 and 10, and when the concentration of the methanol gas is 50ppb-5ppm, the output characteristic curve of the graphene quantum dot functionalized zinc oxide/chlorella composite sensor on methanol also shows good correlation characteristics, the sensitivity on methanol is far higher than that on ethanol, isopropanol, acetone, formaldehyde, benzene, toluene, diethyl ether and ammonia, and the sensitivity is 3 times or more higher than that of other target gases, so that the gas sensor has good selectivity on methanol gas.
Claims (6)
1. The application of the graphene quantum dot/ZnO/chlorella composite film as a sensitive layer on a gas sensor is characterized in that the graphene quantum dot/ZnO/chlorella composite film comprises 15-21% of zinc oxide nano crystal grains, 60-69% of carbonized chlorella, 4-10% of graphene quantum dots and 2-10% of platinum nano particles;
the graphene quantum dots are nitrogen-doped graphene quantum dots, chlorinated graphene quantum dots or sulfur-doped graphene quantum dots;
the particle size of the carbonized chlorella is 200 nm-1 mu m, the size of the zinc oxide nano crystal grain is 3-4 nm, the particle size of the functionalized graphene quantum dot is 4-6 nm, and the particle size of the platinum nano particle is 4-8 nm;
the gas sensor is a methanol gas sensor.
2. The application of the graphene quantum dot/ZnO/chlorella composite film as a sensitive layer on a gas sensor according to claim 1, wherein the preparation method of the graphene quantum dot/ZnO/chlorella composite film comprises the following steps:
(1) Roasting the chlorella under the protection of inert gas to obtain carbonized chlorella;
(2) Preparing platinum nano particles by using chloroplatinic acid, and preparing a platinum nano particle low-carbon alcohol solution;
(3) Adding a zinc precursor and graphene quantum dots into low-carbon alcohol, uniformly stirring, performing ultrasonic dispersion, adding platinum nano particles, and performing ultrasonic dispersion uniformly to obtain a mixed solution;
(4) Rotary evaporating the mixed solution, concentrating to 1/4-1/2 of the original volume, adding carbonized chlorella, and stirring uniformly to obtain a mixed solution;
(5) Spin-coating the mixed solution on a device substrate with interdigital electrodes, heating and drying, and then sequentially carrying out post heat treatment and oxygen plasma treatment to obtain a dried sample;
(6) And (3) placing the dried sample under inert gas for heat treatment to obtain the graphene quantum dot/ZnO/chlorella composite film.
3. The application of the graphene quantum dot/ZnO/chlorella composite film according to claim 2 as a sensitive layer on a gas sensor, wherein the step (2) comprises the following steps:
(21) Adding the materials with the volume ratio of 1:1.2 to 2.4:5, uniformly mixing a chloroplatinic acid solution, a PVP solution and dimethylsulfoxide DMSO, wherein the concentrations of the chloroplatinic acid solution and the PVP solution are 5 multiplied by 10 < -3 > to 5 multiplied by 10 < -2 > mol/L and 1 multiplied by 10 < -4 > to 1 multiplied by 10 < -3 > mol/L respectively;
(22) Adding sodium ascorbate solution with the concentration of 6 multiplied by 10 < -3 > to 6 multiplied by 10 < -2 > mol/L into the mixed solution, heating and stirring, wherein the volume ratio of the sodium ascorbate solution to the chloroplatinic acid solution is 1.5 to 2:1, a step of;
(23) Carrying out centrifugal separation, acetone cleaning and ethanol cleaning on a sample to obtain platinum nano particles;
(24) Dispersing the platinum nano particles into low-carbon alcohol under the action of ultrasound to obtain a platinum nano particle low-carbon alcohol solution.
4. The application of the graphene quantum dot/ZnO/chlorella composite film as a sensitive layer on a gas sensor according to claim 2, wherein the zinc precursor in the step (3) is zinc acetate, zinc acrylate or zinc methacrylate, the graphene quantum dot is nitrogen-doped graphene quantum dot, chlorinated graphene quantum dot or sulfur-doped graphene quantum dot, and the low-carbon alcohol is at least one of ethylene glycol, propanol and isopropanol.
5. The application of the graphene quantum dot/ZnO/chlorella composite film as a sensitive layer on a gas sensor according to claim 2 or 3, wherein the mass ratio of the zinc precursor to the graphene quantum dot in the step (3) is 25-130: 1-5, the mass ratio of the graphene quantum dots to the platinum nano particles is 12-18: 1 to 5.
6. The application of the graphene quantum dot/ZnO/chlorella composite film as a sensitive layer on a gas sensor according to claim 2, wherein the mass ratio of carbonized chlorella to platinum nano particles in the step (4) is 6-12: 1.
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